Toner

Abstract

To provide a toner that has good low-temperature fixing properties and can obtain a good solid image with high gloss and few white spots, in an electrophotographic image forming device that is operated at a higher speed.SOLUTION: A toner has toner particles, the toner containing a crystalline vinyl resin and an amorphous resin, where a weight average particle size of the toner is 4.0 to 12.0 μm, a heat absorption amount ΔH derived from the crystalline vinyl resin is 10 to 70 J / g. When the toner particles are analyzed by time-of-flight secondary ion mass spectrometry while sputtering, an amount of ions of a specific hydrocarbon in a sputtering time required to shave 100 nm of a polymethyl methacrylate standard sample film is A(100), and the amount of ions has one or more peak values, where a maximum value of the peak values is A(dmax), wherein A(dmax) and A(100) satisfy the following formula: 1.5≤A(dmax) / A(100)≤30.0.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to toners used in electrophotography and electrostatic recording. [Background technology]

[0002] In recent years, there has been a widespread demand for even faster process speeds and lower energy consumption in electrophotographic image forming apparatuses. In electrophotographic image forming apparatuses that are even faster, the time required for each step in the electrophotographic process, such as charging, developing, transferring, and fixing, is shortened. In particular, in order to maintain the quality of electrophotographic images, it is important to develop a technology for instantly and uniformly charging toner and a technology for instantly melting and fixing toner. In addition, from the viewpoint of reducing energy consumption, it is required to lower the temperature of the fixing device of electrophotographic image forming apparatuses, and a technology for fixing toner at low temperatures is important. For these reasons, it is more necessary than ever to develop a technology for instantly fixing toner at low temperatures, that is, a technology for so-called "low-temperature fixing property."

[0003] In order to improve the low-temperature fixing property of the toner, there is a method of adding a plasticizer to an amorphous binder resin, as disclosed in Patent Document 1. In addition, in order to further improve the low-temperature fixing property of the toner, there is a technique of using a crystalline resin as a binder resin. The molecular chains of the crystalline resin are regularly arranged, so that the resin hardly softens at a temperature lower than the melting point. Furthermore, when the melting point is exceeded, the crystals melt suddenly, and a sudden drop in viscosity occurs. For this reason, the resin has been attracting attention as a material that has excellent sharp melting properties and improves low-temperature fixing property.

[0004] A toner using a crystalline vinyl resin having a long-chain alkyl group on a side chain in the molecule as the crystalline resin has been proposed. Usually, the crystalline vinyl resin has excellent sharp melting properties due to the long-chain alkyl groups on the side chains crystallizing with each other. Patent Document 2 proposes a toner using two types of crystalline vinyl resins in an emulsion aggregation method. Patent Document 3 proposes a toner in which a crystalline vinyl resin is disposed inside the toner particle and an amorphous vinyl resin is disposed on the surface layer of the toner particle. Patent Document 4 proposes a toner comprising a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer having a different SP value, a core having an island structure made of the amorphous resin, and a shell made of the amorphous vinyl resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2013 / 047296 [Patent Document 2] JP 2002-108018 A [Patent Document 3] JP 2022-163694 A [Patent Document 4] JP 2014-142632 A Summary of the Invention [Problem to be solved by the invention]

[0006] In Patent Document 1, the softening speed of the binder resin is increased while maintaining the glass transition temperature (Tg) of the toner. However, since the toner softens through a step of plasticizing the binder resin after the plasticizer melts, there is a limit to the melting speed of the toner, and it was confirmed that the low-temperature fixability is insufficient in electrophotographic image forming apparatuses with even higher speeds.

[0007] The toner of Patent Document 2 has low-temperature fixing property and durability in electrophotographic devices with higher speeds. It was confirmed that the thermal storage stability was satisfactory. However, it was found that the toner with low charge amount was not printed in part of the solid image, so-called white spots occurred. The inventors speculate that the reason for this is that the toner is made of crystalline vinyl resin from the surface to the inside, making it difficult to retain the charge and therefore difficult to charge uniformly instantaneously. In addition, it was found that it was difficult to achieve a high gloss value in a solid image. The inventors speculate that the reason for this is that the toner contains a large amount of crystalline resin, so that the elasticity at the time of melting is insufficient, and the toner cannot be released uniformly from the fixing roller in a fixing system with a short passing time.

[0008] In Patent Document 3, the toner surface layer contains a large amount of amorphous resin, which allows uniform charging and allows a solid image with fewer white spots to be obtained in a faster electrophotographic image forming apparatus. However, as in Patent Document 2, the toner contains a large amount of crystalline resin, which results in insufficient gloss.

[0009] The toner described in Patent Document 4 has higher elasticity when melted than the toner described in Patent Document 3, but it was found that the gloss was insufficient in electrophotographic image forming apparatuses that were operated at even higher speeds. The present inventors speculate that this is because the presence of a large amount of amorphous resin on the surface layer of the toner makes it difficult to melt the toner uniformly to the inside in a fixing system with a shorter passage time.

[0010] The present disclosure is directed to a toner that has good low-temperature fixing properties and can provide good solid images with high gloss and few white spots in electrophotographic image forming apparatuses that are faster than ever before. [Means for solving the problem]

[0011] One aspect of the present disclosure is a toner having toner particles, The toner contains a crystalline vinyl resin and an amorphous resin, The toner has a weight average particle size of 4.0 to 12.0 μm, the toner has an endothermic heat ΔH derived from the crystalline vinyl resin in differential scanning calorimetry of 10 to 70 J / g; When the toner particles were analyzed by time-of-flight secondary ion mass spectrometry while sputtering for a sputtering time that scraped off 100 nm of a standard polymethyl methacrylate sample film, The amount of ions represented by the following formula (A) during the sputtering time required to remove 100 nm of the standard sample film is defined as A(100), the amount of ions represented by the formula (A) has one or more peak values ​​during the period from the start of measurement to the sputtering time required to remove 100 nm of the standard sample film, The maximum value of the peak values ​​is A(d max ), The A(d max ) and A(100) satisfy the following formula (1): 1.5≦A(d max ) / A(100)≦30.0 (1) -(CH 2 ) n - (A) (In formula (A), n = 18 to 30) Effect of the Invention

[0012] According to one aspect of the present disclosure, it is possible to provide a toner that has good low-temperature fixing properties and can produce good solid images with high gloss and few white spots in an electrophotographic image forming apparatus that is operated at a higher speed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" expressing a numerical range means a numerical range including a lower limit and an upper limit, unless otherwise specified. When specifically stated, the upper and lower limits of each numerical range can be combined in any desired manner. The (meth)acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester. "Monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, one section of carbon-carbon bond in the main chain of a polymer in which a polymerizable monomer is polymerized is considered to be one unit. A polymerizable monomer can be represented by the following formula: [ka]

[0014] [In the formula, R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group); R B represents an optional substituent.] The crystalline resin refers to a resin that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement.

[0015] The toner of the present disclosure will be described in detail below. The present disclosure provides a toner having toner particles, The toner contains a crystalline vinyl resin and an amorphous resin, The toner has a weight average particle size of 4.0 to 12.0 μm, the toner has an endothermic heat ΔH derived from the crystalline vinyl resin in differential scanning calorimetry of 10 to 70 J / g; When the toner particles were analyzed by time-of-flight secondary ion mass spectrometry while sputtering for a sputtering time that scraped off 100 nm of a standard polymethyl methacrylate sample film, The amount of ions represented by the following formula (A) during the sputtering time required to remove 100 nm of the standard sample film is defined as A(100), the amount of ions represented by the formula (A) has one or more peak values ​​during the period from the start of measurement to the sputtering time required to remove 100 nm of the standard sample film, The maximum value of the peak values ​​is A(d max ), The A(d max ) and A(100) satisfy the following formula (1): 1.5≦A(d max ) / A(100)≦30.0 (1) -(CH 2 ) n - (A) (In formula (A), n = 18 to 30)

[0016] In order to solve the above problems, the present inventors have studied a method for controlling the state of existence of crystalline vinyl resin and amorphous resin in a toner. As described above, in the past, as in Patent Document 2, the use of crystalline vinyl resin has been studied from the viewpoint of low-temperature fixability. Also, as in Patent Documents 3 and 4, in order to achieve both chargeability and low-temperature fixability, a crystalline resin has been placed inside the toner and an amorphous resin has been placed on the surface layer of the toner. However, in these methods, in electrophotographic devices with even higher speeds, there is a trade-off between the occurrence of white spots in solid images and a decrease in gloss. Therefore, the present inventors have devised a configuration that can eliminate this trade-off by placing a crystalline vinyl resin on the surface and near the surface of toner particles.

[0017] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by controlling the amounts and states of the crystalline vinyl resin and the amorphous resin in the toner. The amount of crystalline vinyl resin is set within a certain range, and the ratio of the amount of long-chain alkyl inside the toner to the toner surface and near the surface is set within a certain range. This allows the toner surface and near the surface to have an area where a large amount of crystalline vinyl resin is present, allowing the toner to be charged quickly even inside, which is thought to have resulted in good uniform charging properties. In addition, the toner melts instantly into its interior when fixed, and even after melting, the toner maintains a certain degree of elasticity due to the amorphous resin inside the toner. This is thought to result in the toner being crushed uniformly by the fixing roller even when the process speed is very fast, resulting in high gloss. From the above, the inventors believe that the low-temperature fixability is good and the trade-off between the occurrence of white spots and the decrease in gloss has been resolved.

[0018] The toner of the present disclosure has toner particles containing a crystalline vinyl resin and an amorphous resin. The weight average particle diameter of the toner is 4.0 to 12.0 μm. When the weight average particle diameter of the toner is in this range, it becomes easy to control the above formula (1) within the range. From the same viewpoint, the weight average particle diameter of the toner is preferably 5.0 to 10.0 μm, and more preferably 6.0 to 8.5 μm.

[0019] The amount of heat absorbed ΔH derived from the crystalline vinyl resin in differential scanning calorimetry (DSC) of the toner is 10 to 70 J / g. The heat absorption amount ΔH indicates the amount of crystals of the crystalline vinyl resin in the toner. Therefore, when the heat absorption amount ΔH derived from the crystalline vinyl resin is 10 J / g or more, the toner can be instantly melted during fixing in an electrophotographic image forming apparatus with a higher speed, and low-temperature fixing properties can be improved. From the same viewpoint, the heat absorption amount ΔH is preferably 15 J / g or more, and more preferably 20 J / g or more.

[0020] In addition, by making the heat absorption amount ΔH derived from the crystalline vinyl resin 70 J / g or less, the uniform charging property of the toner is improved, and white spots on a solid image can be improved in a faster electrophotographic image forming apparatus. From the same viewpoint, the heat absorption amount ΔH is preferably 60 J / g or less, and more preferably 50 J / g or less. The heat absorption amount ΔH is preferably, for example, 15 to 60 J / g, and more preferably 20 to 50 J / g.

[0021] In addition, since it is easy to improve the heat-resistant storage stability and low-temperature fixability, the endothermic peak derived from the crystalline vinyl resin is preferably in the range of 50.0 to 90.0° C., and more preferably in the range of 50.0 to 80.0° C. The endothermic amount ΔH derived from the crystalline vinyl resin can be controlled by the amount of the crystalline vinyl resin in the toner and the amount of long-chain alkyl in the crystalline vinyl resin.

[0022] The toner particles are analyzed by time-of-flight secondary ion mass spectrometry while sputtering for a sputtering time sufficient to remove 100 nm of a polymethyl methacrylate standard sample film (PMMA standard sample film). At this time, the amount of ions shown by the following formula (A) during the sputtering time sufficient to remove 100 nm of the PMMA standard sample film is designated as A(100). In addition, the amount of ions shown by the following formula (A) has one or more peak values ​​during the period from the start of measurement to the sputtering time sufficient to remove 100 nm of the PMMA standard sample film. Furthermore, the maximum value of the peak values ​​is designated as A(d max), then A(d max ) and A(100) satisfy the following formula (1). 1.5≦A(d max ) / A(100)≦30.0 (1) -(CH 2 ) n - (A) (In formula (A), n = 18 to 30)

[0023] Here, the fact that the amount of ions shown by formula (A) has one or more peak values ​​during the period from the start of measurement to the sputtering time required to remove 100 nm of the PMMA standard sample film indicates that the amount of ions shown by formula (A) changes in the region from the surface of the toner particle to about 100 nm inside the toner particle. Specifically, this indicates that there is a portion in the region from the surface of the toner particle to about 100 nm inside the toner particle where the amount of formula (A) is greater than that at a position about 100 nm inside from the surface of the toner particle. Also, A(d max ) indicates the maximum amount of formula (A) in the region from the surface of the toner particle to about 100 nm inside the toner particle. Also, A(100) indicates the amount of formula (A) at a position about 100 nm inside from the surface of the toner particle.

[0024] Therefore, A(d max A value of A(d ) / A(100) close to 1 indicates that resins with a small amount of formula (A), such as amorphous resins, are abundant in the region from the surface of the toner particles to about 100 nm inside the toner particles. max The value of A(100) being close to 1 indicates that the amount of formula (A) hardly changes from the surface of the toner particle to a depth of about 100 nm inside. Also, A(d max A value of A(100) higher than 1 indicates that the amount of formula (A) is greater on the surface side of the toner particle than at a position about 100 nm inside from the surface of the toner particle.

[0025] A(d maxBy setting the value of A(100) to 1.5 or more, the crystalline vinyl resin unevenly distributed on the toner surface and in its vicinity is instantly charged by rubbing with the charging member, and the generated charge can be retained inside the toner. This results in good uniform charging properties, and allows the production of good solid images with few white spots. In addition, the crystalline vinyl resin on the toner surface and in its vicinity melts instantly during fixing, making it easy to instantly apply heat to the inside of the toner. This makes it possible to crush the toner uniformly on the fixing roller even when the process speed is very fast, resulting in a high-gloss solid image. From a similar perspective, A(d max The value of A(100) is preferably 2.0 or more, and more preferably 2.5 or more.

[0026] Also, A(d max By making the value of A(d ) / A(100) 30.0 or less, the amount of crystalline vinyl resin on the toner surface and in its vicinity is appropriate, preventing charge leakage to other components, etc., and thus improving the charge retention of the toner. This allows the toner to be instantly and uniformly charged, resulting in a good solid image with fewer white spots. From the same perspective, A(d max The value of A(100) is preferably 20.0 or less, and more preferably 12.0 or less.

[0027] A(d max The value of A(100) is preferably from 2.0 to 20.0, and more preferably from 2.5 to 12.0. A(d max The A(100) value can be controlled by the amount of long-chain alkyl on the toner surface and in its vicinity. The A(100) value can be controlled by making the portion with a large amount of crystalline vinyl resin on the surface and in its vicinity very thin, less than 100 nm, and by the ratio of crystalline vinyl resin to amorphous resin inside the toner and the amount of long-chain alkyl in the crystalline vinyl resin. More specifically, for example, in the suspension polymerization method, by increasing the amount of crystalline vinyl resin into which a highly hydrophilic monomer unit is introduced, A(dmax ) / A(100) can be increased. max The value of A(100) / A(100) can be reduced by increasing the amount of long-chain alkyl in the crystalline vinyl resin inside the toner or by reducing the amount of long-chain alkyl in the crystalline vinyl resin on the toner surface and in its vicinity.

[0028] In addition, as described above, the amount of ions represented by formula (A) having one or more peak values ​​indicates that the amount of ions represented by formula (A) is greater in a region from the surface of the toner particle to about 100 nm inside the toner particle than in a position about 100 nm inside the toner particle from the surface. In OF-SIMS analysis, a standard value having a value at least 1.1 times the value of A(100) is defined as a peak. This will be described in detail later. If there is no such peak, when the process speed is very fast, it is difficult to uniformly crush the toner on the fixing roller, and it is difficult to uniformly charge the toner. Therefore, it is difficult to obtain a solid image that combines high gloss and suppression of white spots.

[0029] In order to realize such a peak, the toner surface and the area near it that contains a large amount of crystalline vinyl resin are made thinner than about 100 nm from the surface. Specifically, for example, the amount of crystalline vinyl resin into which a highly hydrophilic monomer unit is introduced during suspension polymerization is controlled.

[0030] A(d max The depth dmax (nm) from the surface of the toner particle at which the unevenness dmax (nm) is observed is preferably from 15 to 90 nm, more preferably from 20 to 75 nm, and further preferably from 25 to 65 nm.

[0031] n in formula (A) indicates that the toner particles have a long-chain alkyl group, and is from 18 to 30 from the viewpoint of adjusting the softening temperature of the toner and improving heat-resistant storage stability and low-temperature fixability. From the same viewpoint, it is preferably from 20 to 26.

[0032] The toner particles preferably contain 15.0 to 70.0% by mass of the crystalline vinyl resin based on the mass of the toner particles. When the toner particles contain 15.0% by mass or more of the crystalline vinyl resin, the melting speed of the toner becomes faster and the low-temperature fixability tends to be improved. From the same viewpoint, the content of the crystalline vinyl resin in the toner particles is more preferably 20.0% by mass or more, and even more preferably 25.0% by mass or more.

[0033] On the other hand, when the toner particles contain 70.0% by mass or less of the crystalline vinyl resin, the elasticity of the toner when melted is increased, and it becomes easier to obtain a high-gloss solid image. From the same viewpoint, the content of the crystalline vinyl resin in the toner particles is more preferably 65.0% by mass or less, and even more preferably 60.0% by mass or less. The content of the crystalline vinyl resin in the toner particles is more preferably from 20.0 to 65.0% by mass, and further preferably from 25.0 to 60.0% by mass.

[0034] The crystalline vinyl resin preferably contains 50.0 to 95.0% by mass of a monomer unit (a) represented by the following formula (a). When the amount of the monomer unit (a) is 50.0% by mass or more, the melting point of the crystalline vinyl resin becomes sharp, and low-temperature fixing property is likely to be good, and a high-gloss solid image is likely to be obtained. From the same viewpoint, the content of the monomer unit (a) is more preferably 55.0% by mass or more, and further preferably 60.0% by mass or more. In addition, when the content of the monomer unit (a) in the crystalline vinyl resin is 95.0% by mass or less, the toner tends to have better uniform charging properties, and a better solid image with fewer white spots is likely to be obtained. From the same viewpoint, the content of the monomer unit (a) is more preferably 90.0% by mass or less, and even more preferably 85.0% by mass or less.

[0035] The content of the monomer unit (a) in the crystalline vinyl resin is preferably from 55.0 to 90.0 mass %, more preferably from 60.0 to 85.0 mass %. [ka] In formula (a), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond, an ester bond or an amide bond, and m represents an integer of 15 to 31. L 1 is preferably an ester bond -COO-, and the carbonyl of the ester bond is R 1 is bonded to the carbon to which it is attached.

[0036] The m in the monomer unit (a) indicates that the crystalline vinyl resin has a long-chain alkyl group, and the presence of the long-chain alkyl group makes the resin more likely to exhibit crystallinity. From the viewpoint of adjusting the softening temperature of the toner and improving the heat-resistant storage stability and low-temperature fixability, the m in the monomer unit (a) is preferably 18 to 30, and more preferably 20 to 26. m can correspond to n in formula (A).

[0037] As a method for introducing the monomer unit (a), there is a method of polymerizing the following (meth)acrylic acid ester in the production of a crystalline vinyl resin. For example, there can be mentioned (meth)acrylic acid esters having an alkyl group having 16 to 32 carbon atoms [cetyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, doriacontyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, etc.].

[0038] The monomer unit (a) may be used alone or in combination of two or more kinds. The crystalline vinyl resin may have other monomer units in addition to the monomer unit (a). A method for introducing other monomer units includes polymerizing the (meth)acrylic acid ester with other vinyl monomers.

[0039] Other vinyl monomers include the following: (Meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Monomers having a urea group: for example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines, Monomers obtained by reacting amines (di-n-ethylamine, di-n-propylamine, di-n-butylamine, etc.), aniline, cycloxylamine, etc.) with isocyanates having 2 to 30 carbon atoms and having an ethylenically unsaturated bond by a known method, etc. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate. Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like. Monomers having an amide group; for example, acrylamide, amines having 1 to 30 carbon atoms and carboxylic acids having 2 to 30 carbon atoms and an ethylenically unsaturated bond (acrylic acid, methacrylic acid, etc.) A monomer obtained by reacting the above by a known method. Monomers having a nitrile group: for example, acrylonitrile, methacrylonitrile, etc. Of these, it is preferable to use styrene, methyl (meth)acrylate, t-butyl (meth)acrylate, and methacrylonitrile.

[0040] The crystalline vinyl resin preferably contains a crystalline vinyl resin A that does not contain a monomer unit (b) represented by the following formula (b), and a crystalline vinyl resin B that contains the monomer unit (b) represented by the formula (b). The toner particles preferably contain 1.5 to 15.0 mass % of the crystalline vinyl resin B.

[0041] In this range, the toner particles contain an appropriate amount of monomer unit (b), and it becomes easy to maintain the charge at the carbonyl group portion, so that the toner has better uniform charging property and it is easy to obtain a better solid image with fewer white spots. From the same viewpoint, the toner particles more preferably contain 2.5 to 12.0 mass % of the crystalline vinyl resin B, and further preferably contain 3.0 to 8.0 mass %. [ka] In formula (b), R 2 represents a hydrogen atom or a methyl group.

[0042] The toner particles contain crystalline vinyl resin A in an amount of preferably 10.0 to 65.0% by mass, more preferably 15.0 to 60.0% by mass, and even more preferably 20.0 to 55.0% by mass. The crystalline vinyl resin A preferably contains the monomer unit (a), a monomer unit based on styrene, and a monomer unit based on (meth)acrylonitrile. The crystalline vinyl resin A preferably contains 40.0 to 90.0 mass% of the monomer unit (a), more preferably 50.0 to 85.0 mass%. The crystalline vinyl resin A preferably contains 1.0 to 40.0 mass% of the monomer unit of styrene, more preferably 2.0 to 30.0 mass%. The crystalline vinyl resin A preferably contains 1.0 to 25.0 mass% of the monomer unit of (meth)acrylonitrile, more preferably 5.0 to 20.0 mass%.

[0043] The crystalline vinyl resin B preferably contains a monomer unit (a), a monomer unit based on styrene, and a monomer unit (b). The crystalline vinyl resin B preferably contains 50.0 to 95.0 mass% of the monomer unit (a), more preferably 60.0 to 92.0 mass%. The crystalline vinyl resin B preferably contains 1.0 to 40.0 mass% of the monomer unit of styrene, more preferably 5.0 to 30.0 mass%. The crystalline vinyl resin B preferably contains 1.0 to 15.0 mass% of the monomer unit (b), more preferably 1.5 to 7.0 mass%.

[0044] The acid value of the crystalline vinyl resin B is preferably 5 to 35 mgKOH / g, and more preferably 10 to 25 mgKOH / g. When the acid value is within the above range, the toner surface and its vicinity can be easily obtained. The thickness of the crystalline vinyl resin can be easily made uniform, the toner can easily have good electrostatic properties, and a good solid image with fewer white spots can easily be obtained.

[0045] The weight average molecular weight (Mw) of the crystalline vinyl resin A is preferably from 10,000 to 50,000, and more preferably from 20,000 to 40,000. The weight average molecular weight (Mw) of the crystalline vinyl resin B is preferably from 5,000 to 50,000, and more preferably from 15,000 to 30,000.

[0046] The toner particles contain a crystalline vinyl resin and an amorphous resin. The toner particles may contain, for example, a crystalline vinyl resin and an amorphous resin as a binder resin. The toner particles preferably contain 20.0 to 70.0% by mass of the amorphous resin. By being in this range, it is easy to control the amount of heat absorption ΔH derived from the crystalline vinyl resin within the above range. From the same viewpoint, the content ratio of the amorphous resin in the toner particles is more preferably 25.0 to 65.0% by mass, and further preferably 30.0 to 60.0% by mass.

[0047] Examples of the amorphous resin include vinyl resin, polyester resin, polyurethane resin, epoxy resin, etc. Since the amorphous resin has a composition similar to that of a crystalline vinyl resin and tends to be well-mixed in the toner, it is preferable that the amorphous resin contains a vinyl resin, and more preferably is a vinyl resin.

[0048] The toner particles preferably contain 25.0 to 65.0 mass % of vinyl resin as the amorphous resin, more preferably 30.0 to 60.0 mass %. When the toner particles contain 25.0 mass % or more of vinyl resin, the composition becomes closer to that of crystalline vinyl resin, and uniform charging property is easily improved, and a better solid image with fewer white spots is easily obtained. In addition, when the toner particles contain 65.0 mass % or less of vinyl resin, low-temperature fixing property is easily improved.

[0049] When the amorphous resin is a vinyl resin, that is, an amorphous vinyl resin, the amorphous vinyl resin preferably has a monomer unit (c) represented by the following formula (c). When the amorphous vinyl resin has the monomer unit (c), it tends to have good compatibility with the crystalline vinyl resin, and the interface between the crystalline vinyl resin and the amorphous resin in the toner tends to become unclear, which tends to further improve the durability of the toner. [ka] In formula (c), R 3 represents a hydrogen atom or a methyl group, and p represents an integer of 3 to 35.

[0050] The preferred range of p is 3 or more and 29 or less, more preferably 3 or more and 19 or less, even more preferably 3 or more and 15 or less, and even more preferably 3 or more and 12 or less. As a method for introducing the monomer unit (c), in addition to the (meth)acrylic acid esters usable in the monomer unit (a), there is a method of polymerizing the following (meth)acrylic acid esters, for example, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, and palmityl (meth)acrylate.

[0051] The monomer unit (c) may be used alone or in combination of two or more kinds. The amorphous vinyl resin may have other monomer units in addition to the monomer unit (c). A method for introducing other monomer units includes a method of polymerizing the (meth)acrylic acid ester with a vinyl monomer that can be used for the crystalline vinyl resin. The amorphous vinyl resin preferably further has a monomer unit of styrene. The amorphous vinyl resin may have a structure crosslinked with a crosslinking agent, such as known crosslinking agents such as hexanediol diacrylate.

[0052] The amorphous vinyl resin preferably contains 5.0 to 40.0% by mass of the monomer unit (c), more preferably 10.0 to 35.0% by mass, and even more preferably 15.0 to 30.0% by mass. The amorphous vinyl resin preferably contains 50.0 to 90.0% by mass, and more preferably 65.0 to 85.0% by mass, of styrene monomer units.

[0053] The toner preferably has a weight average molecular weight (Mw) of tetrahydrofuran (THF) soluble matter measured by gel permeation chromatography (GPC) of 10,000 or more and 200,000 or less. The lower limit is more preferably 30,000 or more, and even more preferably 50,000 or more. The upper limit is more preferably 180,000 or less. By having Mw within the above range, the durability of the toner is more likely to be improved.

[0054] The toner particles may contain a release agent. The release agent is not particularly limited, but is preferably at least one selected from the group consisting of a hydrocarbon wax and an ester wax. By using a hydrocarbon wax and / or an ester wax, it becomes easier to ensure effective release properties. The hydrocarbon wax is not particularly limited, but examples thereof include the following.

[0055] Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch wax, or waxes obtained by oxidizing or adding acids to these.

[0056] The ester wax may be any wax having at least one ester bond in one molecule, and may be either a natural ester wax or a synthetic ester wax. The ester wax is not particularly limited, but examples thereof include the following. Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols and monocarboxylic acids, such as ethylene glycol distearate and hexanediol dibehenate; Esters of trihydric alcohols and monocarboxylic acids, such as glycerin tribehenate; Esters of tetrahydric alcohols and monocarboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; Esters of hexahydric alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate; Esters of polyfunctional alcohols and monocarboxylic acids, such as polyglycerin behenate; natural ester waxes, such as carnauba wax and rice wax;

[0057] Among them, dipentaerythritol hexastearate, dipentaerythritol hexa Esters of hexahydric alcohols and monocarboxylic acids, such as sapalmitate and dipentaerythritol hexabehenate, are preferred.

[0058] The release agent may be a hydrocarbon wax or an ester wax, or may be a combination of a hydrocarbon wax and an ester wax, or may be a mixture of two or more of each. It is preferable to use a hydrocarbon wax alone or two or more of each. It is more preferable that the release agent is a hydrocarbon wax.

[0059] In the toner, the content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 25.0% by mass or less. When the content of the release agent in the toner particles is in the above range, the releasability during fixing is easily ensured. The melting point of the release agent is preferably 60° C. or more and 120° C. or less. When the melting point of the release agent is in the above range, the release agent melts during fixing and easily seeps out onto the toner particle surface, and the release property is easily exhibited. The melting point is more preferably 70° C. or more and 100° C. or less.

[0060] The toner may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, magnetic particles, and the like. In addition, colorants that have been used in conventional toners may be used. Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferably used.

[0061] Magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.Specifically, CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

[0062] Examples of cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

[0063] The colorant may be selected in terms of hue angle, chroma, brightness, light resistance, OHP transparency, and dispersibility in toner particles. When the colorant is not a magnetic particle, the content of the colorant is preferably 1.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, the content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0064] If necessary, a charge control agent may be contained in the toner particles. Alternatively, the charge control agent may be added externally to the toner particles. By blending the charge control agent, it becomes possible to stabilize the charge characteristics and control the amount of triboelectric charge optimally according to the development system. Any known charge control agent can be used as the charge control agent, and a charge control agent that can charge quickly and stably maintain a constant charge amount is particularly preferred.

[0065] As the charge control agent, the following can be mentioned as the agent that controls the toner to be negatively charged. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and and dicarboxylic acid-based metal compounds. Examples of compounds that control the toner to have a positive charge include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorgano tin borates, guanidine compounds, and imidazole compounds. The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100.0 parts by mass of the toner particles.

[0066] The toner particles may be used as they are as a toner, or may be used as a toner by mixing with an external additive, if necessary, and attaching the additive to the surface of the toner particles. The external additive may be an inorganic fine particle selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or a composite oxide thereof, etc. Examples of the composite oxide include silica aluminum fine particles and strontium titanate fine particles. The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less, based on 100 parts by mass of the toner particles.

[0067] The toner particles are not particularly limited in the manufacturing method as long as it is within the scope of the present configuration. The toner may be manufactured by any known method such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, or a pulverization method. From the viewpoint of easily controlling the amount of formula (A) on the toner particle surface and its vicinity, the suspension polymerization method and the emulsion aggregation method are preferred, and the suspension polymerization method is more preferred. That is, the toner particles are preferably suspension polymerization toner particles or emulsion aggregation toner particles, and more preferably suspension polymerization toner particles.

[0068] The suspension polymerization method will now be described in detail. For example, a crystalline vinyl resin (e.g., crystalline vinyl resin A and crystalline vinyl resin B) synthesized in advance is added to a mixture of polymerizable monomers that will produce an amorphous resin (preferably an amorphous vinyl resin). If necessary, other materials such as a colorant, a release agent, and a charge control agent are added and uniformly dissolved or dispersed to prepare a polymerizable monomer composition.

[0069] The polymerizable monomer composition is then dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition, and the polymerizable monomer contained in the particles is then polymerized with an initiator or the like to obtain toner particles. After the polymerization is completed, the toner particles are filtered, washed and dried by known methods, and external additives are added as necessary to obtain the toner.

[0070] The polymerization initiator may be a known polymerization initiator. For example, azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy pivalate, t-butyl peroxy isobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0071] In addition, a known chain transfer agent and a known polymerization inhibitor may be used. The aqueous medium may contain an inorganic or organic dispersion stabilizer. As the dispersion stabilizer, known dispersion stabilizers can be used.

[0072] Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica; and alumina.

[0073] On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, and starch.When using an inorganic compound as a dispersion stabilizer, a commercially available one may be used as is, but in order to obtain finer particles, the inorganic compound may be formed in an aqueous medium and used.For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is recommended to mix an aqueous phosphate solution with an aqueous calcium salt solution under high agitation.

[0074] The aqueous medium may contain a surfactant. As the surfactant, a known surfactant can be used. For example, anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate, cationic surfactants, amphoteric surfactants, and nonionic surfactants can be mentioned.

[0075] The calculation and measurement methods for various physical properties of the toner and toner materials are described below. <Measurement of weight average particle size (D4) of toner> The weight-average particle diameter (D4) of the toner is calculated as follows. The measuring device used is a precision particle size distribution measuring device using the pore electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with an effective measurement channel count of 25,000 channels. The electrolyte solution used for the measurement is one in which special grade sodium chloride is dissolved in ion-exchanged water to a concentration of 1 mass%, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.

[0076] Before performing measurements and analysis, the dedicated software is set as follows. In the "Change standard measurement method (SOMME)" screen of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is set to 1, and the Kd value is set to the value obtained using "Standard particle 10.0 μm" (Beckman Coulter, Inc.). The threshold and noise level are automatically set by pressing the "Threshold / Noise level measurement button." In addition, the current is set to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and "Flush aperture tube after measurement" is checked. In the "Pulse to particle size conversion setting" screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0077] (1) Pour 200 mL of electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture tube flush" function of the dedicated software to remove dirt and air bubbles from inside the aperture tube. (2) Put 30 mL of the electrolyte solution into a 100 mL flat-bottom glass beaker. Add "Conaminon N" (a nonionic surfactant, anionic surfactant, organic builder) as a dispersant. A 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments having a pH of 7 (manufactured by Wako Pure Chemical Industries, Ltd.) is diluted three times by mass with ion-exchanged water and 0.3 mL of the diluted solution is added. (3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees. Pour 3.3 L of ion-exchanged water into the ultrasonic disperser's water tank, and add 2 mL of Contaminon N to this water tank. (4) Set the beaker from (2) above into the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then adjust the height of the beaker so that the resonance state of the electrolyte solution level in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, the electrolytic solution (5) in which the toner is dispersed is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) Analyze the measurement data using the dedicated software that comes with the device to calculate the weight-average particle size (D4). Note that when the dedicated software is set to Graph / Volume%, the "Average diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4).

[0078] <Measuring method for endothermic heat ΔH and melting point due to crystalline vinyl resin in differential scanning calorimetry (DSC) measurement of toner> The endothermic heat ΔH derived from the crystalline vinyl resin is measured under the following conditions using a DSC Q2000 (manufactured by TA Instruments). Heating rate: 10℃ / min Measurement start temperature: 20℃ End of measurement temperature: 180℃ The melting points of indium and zinc are used for temperature correction of the device detection section, and the heat of fusion of indium is used for heat correction. Specifically, 5 mg of sample is weighed out and placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference. The temperature is raised to 180°C at a rate of 10°C / min. The peak temperature and endothermic heat are calculated from each peak.

[0079] When a toner is used as a sample, if the maximum endothermic peak, i.e., the endothermic peak thought to be due to the crystalline vinyl resin, does not overlap with other endothermic peaks such as those of a release agent, the temperature at the maximum endothermic peak can be treated as the melting point of the crystalline vinyl resin, and the endothermic amount ΔH can be calculated.

[0080] On the other hand, when the endothermic peak of another agent such as a release agent overlaps with the maximum endothermic peak, it is necessary to subtract the amount of endotherm attributable to the release agent from the maximum endothermic peak. For example, the endothermic peak derived from the crystalline vinyl resin can be obtained by subtracting the endothermic amount derived from the release agent from the maximum endothermic peak according to the following method. First, the release agent is subjected to a separate DSC measurement to determine its endothermic properties. Next, the release agent content in the toner is determined. The release agent content in the toner can be measured by a known structural analysis. Then, the amount of heat absorption caused by the release agent is calculated from the release agent content in the toner, and this amount is subtracted from the maximum endothermic peak.

[0081] If the release agent is easily compatible with the binder resin components (crystalline vinyl resin and amorphous resin), it is necessary to multiply the content of the release agent by the compatibility rate to calculate the amount of heat absorption caused by the release agent and subtract it. First, mix the molten mixture of the binder resin components and the release agent in the same ratio as the content of the release agent in the toner. The amount of heat absorbed A of the melt-mixed mixture A is calculated. The compatibility ratio is calculated from the value obtained by dividing the amount of heat absorbed A by the theoretical amount of heat absorbed of the mixture A, which is calculated from the amount of heat absorbed by the melt-mixture of the binder resin components and the amount of heat absorbed by the release agent alone, which have been calculated in advance. Theoretical heat absorption of mixture A = heat absorption of the molten mixture of binder resin components alone + heat absorption of the release agent alone Compatibility rate = heat absorption amount A / theoretical heat absorption amount of mixture A Amount of heat absorbed by the release agent = Amount of heat absorbed by the release agent alone × Content of the release agent in mixture A × Compatibility rate Heat absorption amount of crystalline vinyl resin = Heat absorption amount of toner - Heat absorption amount caused by release agent

[0082] The endothermic heat amount ΔH is calculated by using DSC analysis software from a temperature 20.0° C. lower than the corresponding endothermic peak temperature to a temperature 10.0° C. higher than the corresponding endothermic peak temperature. When using a release agent or crystalline vinyl resin separated from a toner, these can be obtained by the procedure described in <Method for separating crystalline vinyl resin and amorphous resin from toner> described later.

[0083] <Measurement method of toner particles using time-of-flight secondary ion mass spectrometry (TOF-SIMS)> TOF-SIMS analysis of toner particles is performed using toner particles obtained by removing external additives from the toner using the following method. A nanoTOF manufactured by ULVAC-PHI, Inc. is used to measure the amount of ions (peak intensity) using TOF-SIMS. The analysis conditions are as follows. Sample preparation: Depositing toner particles onto an indium sheet Sample preparation: None Primary ion: Bi 3 ++ ion Acceleration voltage: 30 kV Charge neutralization mode: On Measurement mode: Positive Raster: 300μm Measurement time: 180s Normally, TOF-SIMS is a surface analysis method, and data in the depth direction is approximately 1 nm. Therefore, the strength inside the toner particles is measured by sputtering the toner particles with argon gas cluster ions and scraping the surface. The relationship with the irradiation time is confirmed in advance by sputtering a PMMA standard sample film under the same conditions to measure the depth.

[0084] The sputtering conditions used this time are as follows: Acceleration voltage: 5 kV Current: 6.0nA Raster: 400μm Irradiation time: 5s The PMMA standard sample film used was manufactured by ULVAC-PHI, Inc. Under these sputtering conditions, it was confirmed that 75 sputterings could remove 100 nm of the PMMA standard sample film, so TOF-SIMS analysis was performed while sputtering was performed up to 75 times.

[0085] <A(d max ) / A(100) calculation method> According to ULVAC-PHI's standard software (Win Cadense), the total count number of 252 to 420, which is the mass number of formula (A), is taken as the amount of ions of structural formula (A) (secondary ion mass / secondary ion charge number (m / z)), and the standard value is calculated by dividing this value by the total amount of ions counted in the toner measurement. Under the above conditions, the standard value measured when sputtering was performed 75 times was defined as A(100). Furthermore, among the standard values ​​measured when sputtering was performed 0 to 74 times, the value of A(100) was The peaks are defined as those that have a value at least 1.1 times larger than the A(d max ) The obtained A(100) and A(d max ), A(d max ) / A(100).

[0086] <Removal of external additives> Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and break up the toner clumps with a spatula or the like. The centrifuge tube is shaken for 30 minutes in a shaker (Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX)) at 350 strokes per minute. After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL) and centrifuged at 58.33 S in a centrifuge (H-9R; Kokusan Co., Ltd.). -1 Centrifugation is performed under the conditions of 100°C, 30 minutes. After centrifugation, the toner particles are present in the top layer of the glass tube, and the external additives are present in the aqueous solution at the bottom. The toner particles in the top layer are collected and filtered, and washed with 2 L of ion-exchanged water heated to 40°C, and the washed toner particles are taken out.

[0087] <Method of measuring molecular weight of toner and crystalline vinyl resin> The molecular weight (weight average molecular weight Mw) of the THF-soluble portion of the toner and the crystalline vinyl resin is measured by gel permeation chromatography (GPC) as follows. First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8 mass%. This sample solution is used to perform measurements under the following conditions. Equipment: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (Showa Denko Co., Ltd.) Eluent: Tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10ml In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (e.g., trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" manufactured by Tosoh Corporation) is used.

[0088] <Method of separating crystalline vinyl resins A and B, and amorphous resin from toner> The crystalline vinyl resins A and B, and the amorphous resin can be separated from the toner by a known method, and an example will be shown below. Gradient LC is used as a method for separating resin components from toner. In this analysis, separation can be performed according to the polarity of the resin in the binder resin, regardless of molecular weight. First, the toner is dissolved in chloroform. The sample concentration is adjusted to 0.1 mass% with chloroform, and the solution is filtered through a 0.45 μm PTFE filter and used for measurement. The gradient polymer LC measurement conditions are shown below. Equipment: UlTIMATE3000 (Thermo Fisher Scientific) Mobile phase: A Chloroform (HPLC), B Acetonitrile (HPLC) Gradient: 2min (A / B=0 / 100) → 25min (A / B=100 / 0) The gradient of the change in the mobile phase was made linear. Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6mmφx150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Aerosol Detector (Corona-CAD) (Therm o Fisher Scientific)

[0089] In the time-intensity graph obtained by the measurement, the resin components can be separated into peaks according to their polarity. After that, the above measurement is performed again, and the resins can be separated by taking out the fractions at the time when each peak reaches its valley. DSC measurement is performed on the separated resins, and resins with a melting point peak are classified as crystalline vinyl resins, and resins without a melting point peak are classified as amorphous resins. In the examples described later, the acid value of the separated crystalline vinyl resin was measured, and a resin having an acid value of less than 0.5 mgKOH / g was designated as crystalline vinyl resin A, and a resin having an acid value of 0.5 mgKOH / g or more was designated as crystalline vinyl resin B. The method for measuring the acid value will be described later.

[0090] If the toner contains a release agent, it is necessary to separate the release agent from the toner. The release agent is separated by recycling HPLC to separate components with a molecular weight of 2000 or less as the release agent. The measurement method is as follows. First, a chloroform solution of the toner is prepared by the method described above. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in chloroform is 1.0 mass %. This sample solution is used to perform measurements under the following conditions. ·Equipment: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) Column: JAIGEL 2H, 4H (Japan Analytical Industry Co., Ltd.) Eluent: Chloroform ·Flow rate: 10.0ml / min Oven temperature: 40.0℃ Sample injection volume: 1.0ml In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (e.g., trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" manufactured by Tosoh Corporation) is used. From the molecular weight curve thus obtained, components having a molecular weight of 2000 or less are repeatedly separated and the release agent is removed from the toner.

[0091] <Method for measuring the content of various monomer units in resin> The content ratio of various monomer units in a resin is measured as follows: 1 H-NMR was performed under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times: 64 Measurement temperature: 30℃ Sample: 50 mg of the sample to be measured was placed in a sample tube with an inner diameter of 5 mm, and heavy water was added as the solvent. Chloroform (CDCl 3 ) is added and dissolved in a thermostatic bath at 40°C. 1 The H-NMR chart is analyzed to identify the structure of each monomer unit. As an example, the measurement of the content ratio of monomer unit (a) in a crystalline vinyl resin is described here. 1 In the H-NMR chart, a peak that is independent of the peaks that are attributable to the components of the monomer unit (a) is selected from the peaks that are attributable to the components of the other monomer units, and the integral value S1 of this peak is calculated. The integral values ​​of the other monomer units contained in the crystalline vinyl resin are also calculated in the same manner.

[0092] When the monomer units constituting the crystalline vinyl resin are the monomer unit (a) and one other monomer unit, the content of the monomer unit (a) is calculated using the above integral value S1 and the integral value S2 of the peak of the other monomer unit as follows: where n1 and n2 are the numbers of hydrogen atoms in the constituent elements to which the peaks of interest for each site belong. Content of monomer unit (a) (mol%)= {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100 Even when two or more other monomer units are present, the content of the monomer unit (a) can be calculated in the same manner.

[0093] In addition, when a polymerizable monomer that does not contain a hydrogen atom in any component other than the vinyl group is used, 13 Measure nuclei using C-NMR 13 C, and the measurement was performed in single pulse mode. 1 The content of each monomer unit is converted to mass % by multiplying the proportion (mol %) of each monomer unit calculated by the above method by the molecular weight of each monomer unit. The amorphous resin is also measured in the same manner.

[0094] <Measurement of resin acid value> The acid value is the mass (mg) of potassium hydroxide required to neutralize the acid contained in 1 g of a sample. The acid value of a resin is measured in accordance with JIS K 0070-1992, and specifically, is measured according to the following procedure. (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., leave for 3 days, then filter to obtain a potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is calculated by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, and then calculating the amount of the potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0095] (2) Operation (A) Main Test Weigh out 2.0 g of the crushed sample into a 200 mL Erlenmeyer flask, add 100 mL of a toluene / ethanol (2:1) mixed solution, and dissolve for 5 hours. Next, add a few drops of the above phenolphthalein solution as an indicator, and titrate with the above potassium hydroxide solution. The end point of the titration is when the indicator remains a pale red color for 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used). (3) The obtained result is substituted into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0096] <Measurement of the content ratio of crystalline vinyl resin, crystalline vinyl resin A, crystalline vinyl resin B, and amorphous resin> The content ratios of the crystalline vinyl resin, crystalline vinyl resin A, crystalline vinyl resin B, and amorphous resin in the toner are calculated using the separation by the gradient polymer LC measurement described above. Specifically, the weight of each resin obtained is measured and divided by the toner weight. EXAMPLES

[0097] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In the following formulations, the parts are by weight unless otherwise specified.

[0098] (Preparation of Crystalline Vinyl Resin A1) The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following monomers in the ratio shown below.) (Behenyl acrylate (monomer (a)) 70.0 parts) (12.0 parts styrene) (Methacrylonitrile 18.0 parts) Polymerization initiator: 0.5 parts t-butyl peroxypivalate (NOF Corp.: Perbutyl PV) The inside of the reaction vessel was heated to 70°C while stirring at 200 rpm, and polymerization reaction was carried out for 12 hours, to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Then, the temperature of the solution was lowered to 25°C, and the solution was poured into 1000.0 parts of methanol while stirring, to precipitate the methanol insoluble matter. The obtained methanol insoluble matter was filtered, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain crystalline vinyl resin A1. The weight average molecular weight (Mw) of the obtained crystalline vinyl resin A1 was 30000, and the melting point was 60°C.

[0099] (Preparation of Crystalline Vinyl Resins A2 to A15) Crystalline vinyl resins A2 to A15 were prepared in the same manner as in the preparation of crystalline vinyl resin A1, except that the amount of the monomer composition added was changed to that shown in Table 1 and the molecular weight was controlled by the amount of polymerization initiator.

[0100] [Table 1]

[0101] (Preparation of Crystalline Vinyl Resin B1) The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following monomers in the ratio shown below.) (Behenyl acrylate (monomer (a)) 70.0 parts) (25.0 parts styrene) (Methacrylic acid (monomer (b)) 5.0 parts) Polymerization initiator: 0.5 parts t-butyl peroxypivalate (NOF Corp.: Perbutyl PV) The inside of the reaction vessel was heated to 70°C while stirring at 200 rpm, and polymerization reaction was carried out for 12 hours, to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Then, the temperature of the solution was lowered to 25°C, and the solution was poured into 1000.0 parts of methanol while stirring, to precipitate the methanol insoluble matter. The obtained methanol insoluble matter was filtered, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain crystalline vinyl resin B1. The weight average molecular weight (Mw) of the obtained crystalline vinyl resin B1 was 20000, the melting point was 60°C, and the acid value was 15 mgKOH / g.

[0102] (Preparation of Crystalline Vinyl Resins B2 to B8 and Amorphous Resins 1 and 2) Crystalline vinyl resins B2 to B8 and amorphous resins 1 and 2 were obtained in the same manner as in the preparation of crystalline vinyl resin B1, except that the amount of the monomer composition added was changed to that shown in Table 2.

[0103] [Table 2]

[0104] (Preparation of amorphous resin 3) Bisphenol A propylene oxide adduct (2.2 mol adduct) 60.0 parts Bisphenol A ethylene oxide adduct (2.2 mol adduct) 40.0 parts Terephthalic acid 77.0 parts Trimellitic acid 2.0 parts The polyester monomer mixture was charged into a 5-liter autoclave together with 0.05% by mass of tetraisobutyl titanate relative to the total amount. A reflux condenser, a moisture separator, a nitrogen gas inlet tube, a thermometer, and a stirrer were attached, and a polycondensation reaction was carried out at 230°C while introducing nitrogen gas into the autoclave. After the reaction was completed, the product was removed from the vessel, cooled, and pulverized to obtain amorphous resin 3. The glass transition temperature Tg of amorphous resin 3 was 60°C, and the weight average molecular weight (Mw) was 26,000.

[0105] (Preparation of amorphous resin 4) The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following monomers in the ratio shown below.) (Butyl acrylate 25.0 parts) (Styrene 75.0 parts) Polymerization initiator: t-butyl peroxypivalate (NOF Corp.: Perbutyl PV) 0.4 parts The inside of the reaction vessel was heated to 70°C while stirring at 200 rpm, and a polymerization reaction was carried out for 12 hours, to obtain a solution in which a polymer of the monomer composition was dissolved in toluene. The solution was then cooled to 25°C, and then the solution was poured into 1000.0 parts of methanol while stirring, to precipitate the methanol insoluble matter. The obtained methanol insoluble matter was filtered, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain amorphous resin 4. The glass transition temperature Tg of amorphous resin 4 was 60°C, and the weight average molecular weight (Mw) was 50,000.

[0106] <Production of Toner 1> [Toner production by suspension polymerization method] (Adjustment of toner particles 1) Butyl acrylate 15.0 parts Styrene 45.0 parts Colorant Pigment Blue 15:3 6.5 parts The mixture was placed in an attritor (manufactured by Nippon Coke Corporation) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion. On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix Corporation) and a thermometer, and the temperature was raised to 60 ° C. while stirring at 12000 rpm. An aqueous calcium chloride solution in which 9.0 parts of calcium chloride (2-hydrate) was dissolved in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60 ° C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0107] Next, the raw material dispersion liquid was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm. Crystalline vinyl resin A1 40.0 parts Crystalline vinyl resin B1 5.0 parts Release agent 1 9.0 parts (Release agent 1: DP18 (dipentaerythritol stearate wax, melting point 79°C, manufactured by Nisshin Oillio Co., Ltd.) After adding 5.0 parts of t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corp.) as a polymerization initiator and stirring for another minute, the mixture was poured into the aqueous medium being stirred at 12,000 rpm with the high-speed stirring device. Stirring was continued for 20 minutes at 12,000 rpm with the high-speed stirring device while maintaining the temperature at 60°C, to obtain a granulation liquid.

[0108] The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and heated to 70° C. while stirring at 150 rpm under a nitrogen atmosphere. A polymerization reaction was carried out at 150 rpm for 12 hours while maintaining the temperature at 70° C., to obtain a toner particle dispersion liquid. The resulting toner particle dispersion was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Dilute hydrochloric acid was then added while maintaining the stirring until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered off, thoroughly washed with ion-exchanged water, and vacuum-dried at 30°C for 24 hours to obtain toner particles 1.

[0109] (Preparation of Toner 1) For the above toner particles, 1:98.0 parts, silica fine particles (hydrophobized with hexamethyldisilazane, number-average particle size of primary particles: 10 nm, BET specific surface area: 170 m) were added as an external additive. 2 The mixture was mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Corporation) to obtain toner 1. The obtained toner 1 was analyzed by the above-mentioned method, and the weight average particle diameter (D4) was 7.0 μm, the heat absorption amount ΔH was 30 J / g, and the weight average molecular weight (Mw) was 100,000. max ) / A(100) is 3.2, and the peak position of the formula (A) (d max ) was 40 nm from the toner particle surface (30 sputterings). The amount of each resin in the toner particles and the monomer unit in the crystalline vinyl resin were measured from the obtained toner, and the content ratio was the same as that of the charge. The results are shown in Table 4.

[0110] [Table 3]

[0111] [Table 4] In the table, dmax (nm) is A(d max ) is observed from the toner particle surface. "Amount of crystalline vinyl resin", "Amount of crystalline vinyl resin B", "Amount of amorphous resin" and "Amount of amorphous vinyl resin" indicate the content ratio in the toner particle.

[0112] <Production of Toners 2 to 8 and 10 to 21> In the preparation of toner particle 1, the type and amount of polymerizable monomer used were changed as shown in Table 3, and the same procedure was repeated to obtain toner particles 2 to 8 and 10 to 21. Furthermore, external addition was carried out in the same manner as for Toner 1 to obtain Toners 2 to 8 and 10 to 21. The physical properties of the toners are shown in Table 4. The amounts of each resin in the toner particles and the monomer units in the crystalline vinyl resin were measured from the obtained toners, and the content ratios were the same as those of the charged materials. The results are shown in Table 4.

[0113] <Production of Toner 9> Toner 9 was obtained in the same manner as in the production of Toner 1, except that the charges of butyl acrylate and styrene were changed as shown in Table 3, and amorphous resin 3 and 0.1 parts of hexanediol diacrylate were added when Crystalline vinyl resin A5, Crystalline vinyl resin B5, and Release agent 1 were added. The physical properties of Toner 9 obtained are shown in Table 4.

[0114] <Production of Toner 21> [Toner production by emulsion aggregation method] (Preparation of Crystalline Vinyl Resin A12 Dispersion) Toluene 300.0 parts Crystalline vinyl resin A12 100.0 parts The above materials were weighed, mixed, and dissolved at 90°C. Separately, 5.0 parts of sodium dodecylbenzenesulfonate in 700.0 parts of ion-exchanged water, 10.0 parts of sodium laurate was added and dissolved by heating at 90°C. The toluene solution and the aqueous solution were then mixed and stirred at 7000 rpm using an ultra-high speed stirring device TK Robomix (manufactured by Primix). Furthermore, the mixture was emulsified at a pressure of 200 MPa using a high-pressure impact dispersing device Nanomizer (manufactured by Yoshida Kikai Kogyo). After that, the toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain a crystalline resin dispersion liquid with a concentration of 20% of crystalline vinyl resin A12 fine particles. The 50% particle size (D50) based on volume distribution of the crystalline vinyl resin A12 fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

[0115] (Preparation of Crystalline Vinyl Resin B5 Dispersion) A crystalline vinyl resin B5 dispersion having a concentration of crystalline vinyl resin B5 fine particles of 20% was obtained in the same manner as in the preparation of the crystalline vinyl resin A12 dispersion, except that the crystalline vinyl resin A12 was changed to crystalline vinyl resin B5. The 50% particle size (D50) based on volume distribution of the crystalline vinyl resin B5 fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

[0116] (Preparation of amorphous resin dispersion) In the same manner as in the preparation of the crystalline vinyl resin A12 dispersion, except that the crystalline vinyl resin A12 was changed to amorphous resin 4, an amorphous resin dispersion having a concentration of amorphous resin 4 fine particles of 20% was obtained. The 50% particle size (D50) based on volume distribution of the amorphous resin fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.38 μm.

[0117] (Preparation of release agent dispersion) Release agent 1 100.0 parts Anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5.0 parts Ion-exchanged water 395.0 parts The above materials were weighed and placed in a mixing vessel equipped with an agitator, then heated to 90°C and circulated through a Clearmix W Motion (manufactured by M Technique) for 60 minutes to perform dispersion processing. The dispersion processing conditions were as follows: Rotor outer diameter 3cm Clearance 0.3mm Rotor speed: 19000 r / min Screen rotation speed: 19000 r / min After the dispersion treatment, the mixture was cooled to 40° C. under cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10° C. / min, to obtain a release agent dispersion liquid with a release agent fine particle concentration of 20%. The 50% particle size (D50) based on the volume distribution of the release agent fine particles was measured using a dynamic light scattering particle size distribution meter Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

[0118] (Preparation of Colorant Dispersion) Coloring agent 50.0 parts (Cyan pigment made by Dainichi Seika: Pigment Blue 15:3) Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 7.5 parts Ion-exchanged water 442.5 parts The above materials were weighed, mixed, dissolved, and dispersed using a high-pressure impact dispersing machine, Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). The colorant was dispersed for 1 hour using a dispersing agent, to obtain a colorant dispersion liquid having a concentration of 10% colorant fine particles. The 50% particle size (D50) based on the volume distribution of the colorant fine particles was measured using a dynamic light scattering particle size distribution meter Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

[0119] (Adjustment of Toner 21) Crystalline vinyl resin A12 dispersion 425.0 parts Crystalline vinyl resin B5 dispersion 50.0 parts ·Amorphous resin dispersion liquid 75.0 parts Release agent dispersion 45.0 parts Colorant dispersion 65.0 parts Ion-exchanged water 160.0 parts The above materials were put into a round stainless steel flask and mixed. Then, they were dispersed for 10 minutes at 5000 rpm using a homogenizer Ultra Turrax T50 (manufactured by IKA). After adding a 1.0% aqueous nitric acid solution and adjusting the pH to 3.0, the mixture was heated to 58°C in a heating water bath using a stirring blade while appropriately adjusting the rotation speed so that the mixture was stirred.

[0120] The volume average particle size of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III, and when aggregated particles with a weight average particle size (D4) of 6.0 μm were formed, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution. Then, while continuing to stir, the mixture was heated to 75° C. The aggregated particles were fused by maintaining the mixture at 75° C. for 1 hour. Thereafter, the mixture was cooled to 45° C. and heat-treated for 5 hours. Thereafter, the mixture was cooled to 25° C., filtered, and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the mixture was dried using a vacuum dryer to obtain toner particles 21. The same external additions as in Toner 1 were made to Toner Particles 21 to obtain Toner 21. The physical properties of Toner 21 are shown in Table 4.

[0121] <Production of Comparative Toner 1> (Preparation of Crystalline Vinyl Resin A13 Dispersion) A crystalline vinyl resin A13 dispersion having a concentration of crystalline vinyl resin A13 fine particles of 20% was obtained in the same manner as in the preparation of the crystalline vinyl resin A12 dispersion, except that the crystalline vinyl resin A12 was changed to crystalline vinyl resin A13.

[0122] (Preparation of Crystalline Vinyl Resin B7 Dispersion) A crystalline vinyl resin B7 dispersion having a concentration of crystalline vinyl resin B7 fine particles of 20% was obtained in the same manner as in the preparation of the crystalline vinyl resin A12 dispersion, except that the crystalline vinyl resin A12 was changed to crystalline vinyl resin B7.

[0123] (Adjustment of Comparative Toner 1) Crystalline vinyl resin A13 dispersion 500.0 parts Crystalline vinyl resin B7 dispersion 125.0 parts Release agent dispersion 45.0 parts Colorant dispersion 65.0 parts Ion-exchanged water 160.0 parts Comparative toner 1 was obtained in the same manner as in preparation of toner 21, except that the above-mentioned preparation was changed. In TOF-SIMS analysis of comparative toner 1, no peak of structural formula (A) was observed even after 75 sputterings under the above-mentioned conditions. After an additional 75 sputterings, a peak was observed at 177 nm (133 sputterings).

[0124] <Production of Comparative Toners 2 to 8> Comparative toner particles 2 to 8 were obtained in the same manner as in the preparation of toner particles 1 in the production of toner 1, except that the type and amount of polymerizable monomer used were changed as shown in Table 3. Furthermore, external addition was carried out in the same manner as for toner 1 to obtain comparative toners 2 to 8. The physical properties of the toners are shown in Table 4. In comparative toners 2 and 3, the maximum amount of formula (A) was less than 1.1 times A(100), and did not reach a peak.

[0125] <Production Example of Comparative Toner 9> Crystalline vinyl resin A3 50.0 parts Crystalline vinyl resin B2 5.0 parts Amorphous resin 4 50.0 parts Release agent 1 9.0 parts Colorant Pigment Blue 15:3 6.5 parts The above materials were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 5 minutes, the mixture was kneaded at a discharge temperature of 120°C in a twin-screw kneader (PCM-30, Ikegai Corporation) set at a temperature of 110°C. The kneaded mixture was cooled and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed product. The coarsely crushed product was finely crushed using a mechanical crusher (T-250, Freund Turbo Corporation). Classification was then performed using a Faculty F-300 (Hosokawa Micron Corporation) to obtain toner particles. The operating conditions were a classifying rotor rotation speed of 130 s -1 , Dispersion rotor speed 120s -1 It was decided. The obtained toner particles were subjected to a heat treatment using a surface treatment device to obtain heat-treated toner particles. The operating conditions were a feed rate of 3 kg / hr, a hot air temperature of 130° C., and a hot air flow rate of 6 m 3 / min., cold air temperature = -5℃, cold air flow rate = 4m 3 / min., Blower air volume = 20m 3 / min., Injection air flow rate = 1m 3 The same external additions as in Toner 1 were carried out on the obtained toner particles to obtain Comparative Toner 9. In the TOF-SIMS analysis of Comparative Toner 9, no peak of structural formula (A) was observed even after 75 sputterings under the above conditions. After an additional 75 sputterings, no peak was observed up to 200 nm.

[0126] <Example 1> The process cartridge filled with toner 1 was left for 48 hours at 25°C and 40% RH. Using an LBP-712Ci that had been modified so that it could operate even without the fixing unit, an unfixed image was printed with an image pattern in which 9 10mm x 10mm square images were evenly arranged on the entire transfer paper. The amount of toner on the transfer paper was 0.80mg / cm. 2 The fixing start temperature was evaluated. The transfer paper is A4 regular paper ("Proverbond paper": 105 g / m 2 , manufactured by Fox River) and A4 gloss paper ("BROCHURE PAPER 150g GLOSSY paper" manufactured by Hewlett-Packard: 150g / m 2 The fixing unit used was an external fixing unit that had been removed from the LBP-712Ci and was able to operate outside the laser beam printer.

[0127] <Toner Evaluation Method> <1> Low temperature fixability The fixing temperature of the external fixing unit was raised in 5°C increments from 100°C, and fixing was performed on normal paper at a process speed of 330 mm / sec. Kimwipe (S-200, manufactured by Crecia Co., Ltd.) was used, and the pressure was 7.35 kPa (75 g / cm 2The fixed image is rubbed 10 times with a load of 10 ... The initial temperature was evaluated based on the following criteria, with C or higher being considered good. The evaluation results are shown in Table 5. [Evaluation Criteria] A: Fixing start temperature is 110℃ or less B: Fixing start temperature is 115℃ or higher and 120℃ or lower C: Fixing start temperature is 125℃ or higher and 130℃ or lower D: Fixing start temperature is 135°C or higher

[0128] <2> White Spot the above <1> Ten sheets of fixed images at the fixing start temperature in the evaluation were used. The number of white spots in the obtained 10 fixed images was evaluated based on the following criteria, and C or higher was judged to be good. The evaluation results are shown in Table 5. [Evaluation Criteria] A: Less than 5 white dots B: The number of white dots is 5 or more but less than 10 C: 10 or more but less than 15 white dots D: 15 or more white dots

[0129] <3> Gross the above <1> The gloss paper was fixed at a temperature 20° higher than the fixing start temperature in the evaluation, and at a process speed of 330 mm / sec. The gloss value was measured using a handy gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions were set at a projection angle and a receiving angle of 75°, and all image patterns arranged in 9 points were measured and the average value was evaluated. The average gloss value was evaluated based on the following criteria, with C or above being considered good. The evaluation results are shown in Table 5. [Gross evaluation criteria] A: Gross average value is 60 or more B: Gross average value is 50 or more and less than 60 C: Gross average value is between 40 and 50 D: Gross average value is less than 40

[0130] <Examples 2 to 21 and Comparative Examples 1 to 9> The toner was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0131] [Table 5]

[0132] The present disclosure relates to the following configurations. (Configuration 1) A toner having toner particles, The toner contains a crystalline vinyl resin and an amorphous resin, The toner has a weight average particle size of 4.0 to 12.0 μm, the toner has an endothermic heat ΔH derived from the crystalline vinyl resin in differential scanning calorimetry of 10 to 70 J / g; When the toner particles were analyzed by time-of-flight secondary ion mass spectrometry while sputtering for a sputtering time that scraped off 100 nm of a standard polymethyl methacrylate sample film, The amount of ions represented by the following formula (A) during the sputtering time required to remove 100 nm of the standard sample film is defined as A(100), the amount of ions represented by the formula (A) has one or more peak values ​​during the period from the start of measurement to the sputtering time required to remove 100 nm of the standard sample film, The maximum value of the peak values ​​is A(d max ), The A(d max ) and A(100) satisfy the following formula (1): 1.5≦A(d max ) / A(100)≦30.0 (1) -(CH 2 ) n - (A) (In formula (A), n = 18 to 30) (Configuration 2) 2. The toner according to claim 1, wherein the toner particles contain the crystalline vinyl resin in an amount of 15.0 to 70.0% by mass. (Configuration 3) 3. The toner according to configuration 1 or 2, wherein the crystalline vinyl resin contains 50.0 to 95.0% by mass of a monomer unit (a) represented by the following formula (a): TIFF2024073163000010.tif44153 [In formula (a), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond, an ester bond or an amide bond, and m represents an integer of 15 to 31. (Configuration 4) The toner according to any one of configurations 1 to 3, wherein the toner particles contain the amorphous resin in an amount of 20.0 to 70.0% by mass. (Configuration 5) the amorphous resin comprises a vinyl resin, 5. The toner according to any one of Configurations 1 to 4, wherein the toner particles contain the vinyl resin as the amorphous resin in an amount of 25.0 to 65.0% by mass. (Configuration 6) The crystalline vinyl resin is A crystalline vinyl resin A not containing a monomer unit (b) represented by the following formula (b), A crystalline vinyl resin B containing a monomer unit (b) represented by the following formula (b), Including, The toner according to any one of configurations 1 to 5, wherein the toner particles contain the crystalline vinyl resin B in an amount of 1.5 to 15.0% by mass. TIFF2024073163000011.tif49168 [In formula (b), R 2 represents a hydrogen atom or a methyl group. (Configuration 7) The above A(d max 7. The toner according to any one of configurations 1 to 6, wherein a depth dmax (nm) from the surface of the toner particle at which the unevenness is observed is 20 to 75 nm.

Claims

1. 1. A toner having toner particles, The toner contains a crystalline vinyl resin and an amorphous resin, The weight average particle diameter of the toner is 4.0 to 12.0 μm, the toner has an endothermic heat ΔH attributed to the crystalline vinyl resin in differential scanning calorimetry measurement of 10 to 70 J / g; When the toner particles were analyzed by time-of-flight secondary ion mass spectrometry while sputtering was continued for a sputtering time sufficient to remove 100 nm from a polymethyl methacrylate standard sample film, The amount of ions shown by the following formula (A) during the sputtering time required to remove 100 nm of the standard sample film is defined as A(100), the amount of ions represented by the formula (A) has one or more peak values ​​during the period from the start of measurement to the sputtering time required to remove 100 nm of the standard sample film, The maximum value of the peak values ​​is A(d ｍａｘ ) and The A(d ｍａｘ ) and A(100) satisfy the following formula (1): 1.5≦A(d ｍａｘ ) / A(100)≦30.0 ・・・(1) -(CH ２ ) ｎ - ・・・(A) (In formula (A), n=18 to 30)

2. 2. The toner according to claim 1, wherein the toner particles contain the crystalline vinyl resin in an amount of 15.0 to 70.0% by mass.

3. 3. The toner according to claim 1, wherein the crystalline vinyl resin contains 50.0 to 95.0% by mass of a monomer unit (a) represented by the following formula (a): [In formula (a), R １ represents a hydrogen atom or a methyl group, L １ represents a single bond, an ester bond, or an amide bond, and m represents an integer of 15 to 31.

4. 3. The toner according to claim 1, wherein the toner particles contain the amorphous resin in an amount of 20.0 to 70.0% by mass.

5. the amorphous resin includes a vinyl resin, 3. The toner according to claim 1, wherein the toner particles contain the vinyl resin as the amorphous resin in an amount of 25.0 to 65.0% by mass.

6. The crystalline vinyl resin is a crystalline vinyl resin A that does not contain a monomer unit (b) represented by the following formula (b); a crystalline vinyl resin B containing a monomer unit (b) represented by the following formula (b); Including, 3. The toner according to claim 1, wherein the toner particles contain the crystalline vinyl resin B in an amount of 1.5 to 15.0% by mass. [In formula (b), R ２ represents a hydrogen atom or a methyl group.

7. The A(d ｍａｘ 3. The toner according to claim 1, wherein the depth dmax (nm) from the surface of the toner particle at which the above-mentioned phenomenon is observed is 20 to 75 nm.

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